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Interdependent iron and phosphorus availability controls photosynthesis through retrograde signaling

Abstract Iron deficiency hampers photosynthesis and is associated with chlorosis. We recently showed that iron deficiency-induced chlorosis depends on phosphorus availability. How plants integrate these cues to control chlorophyll accumulation is unknown. Here, we show that iron limitation downregulates photosynthesis genes in a phosphorus-dependent manner. Using transcriptomics and genome-wide association analysis, we identify two genes, PHT4;4 encoding a chloroplastic ascorbate transporter and bZIP58 , encoding a nuclear transcription factor, which prevent the downregulation of photosynthesis genes leading to the stay-green phenotype under iron-phosphorus deficiency. Joint limitation of these nutrients induces ascorbate accumulation by activating expression of an ascorbate biosynthesis gene, VTC4 , which requires bZIP58. Furthermore, we demonstrate that chloroplastic ascorbate transport prevents the downregulation of photosynthesis genes under iron-phosphorus combined deficiency through modulation of ROS homeostasis. Our study uncovers a ROS-mediated chloroplastic retrograde signaling pathway to adapt photosynthesis to nutrient availability.

59 BASIC BIOLOGICAL SCIENCES↗

Soil properties explain tree growth and mortality, but not biomass, across phosphorus-depleted tropical forests

We observed strong positive relationships between soil properties and forest dynamics of growth and mortality across twelve primary lowland tropical forests in a phosphorus-poor region of the Guiana Shield. Average tree growth (diameter at breast height) increased from 0.81 to 2.1 mm yr -1 along a soil texture gradient from 0 to 67% clay, and increasing metal-oxide content. Soil organic carbon stocks in the top 30cm ranged from 30 to 118 tons C ha -1 , phosphorus content ranged from 7 to 600 mg kg -1 soil, and the relative abundance of arbuscular mycorrhizal fungi ranged from 0 to 50%, all positively correlating with soil clay, and iron and aluminum oxide and hydroxide content. In contrast, already low extractable phosphorus (Bray P) content decreased from 4.4 to <0.0 mg kg -1 in soil with increasing clay content. A greater prevalence of arbuscular mycorrhizal fungi in more clayey forests that had higher tree growth and mortality, but not biomass, indicates that despite the greater investment in nutrient uptake required, soils with higher clay content may actually serve to sustain high tree growth in tropical forests by avoiding phosphorus losses from the ecosystem. Our study demonstrates how variation in soil properties that retain carbon and nutrients can help to explain variation in tropical forest growth and mortality, but not biomass, by requiring niche specialization and contributing to biogeochemical diversification across this region.

54 ENVIRONMENTAL SCIENCES↗

Climate warming enhances biodiversity and stability of grassland soil phosphorus-cycling microbial communities

Abstract Climate warming poses significant challenges to global phosphorus sustainability, an essential component of Earth biogeochemistry cycling and water-food-energy nexus. Despite the crucial role of polyphosphate-accumulating organism as key functional microbial agents in phosphorus cycling, the impacts of global climate warming on polyphosphate accumulating organism communities remain largely enigmatic. This study investigates the effects of climate warming on the taxonomic, network, and functional profiles of soil bacterial polyphosphate-accumulating organisms, leveraging fluorescence-activated cell sorting and single-cell Raman spectroscopy. Climate warming enhances both taxonomic and functional biodiversity of polyphosphate-accumulating organisms via biotic interactions and environmental filtering, with observed functionality-biodiversity relationships supporting the functional redundancy theory. Furthermore, polyphosphate-accumulating organism network complexity and stability rise under warming with strengthened positive relationships, supporting stress gradient hypothesis and the belief that complexity begets stability. Finally, polyphosphate-accumulating organisms are significantly correlated to key ecosystem functioning in carbon and phosphorus cycling under warming. Our study suggests that preserving polyphosphate-accumulating organism communities is crucial for maintaining soil ecosystem functioning and sustainable phosphorus management in a warming world and opens avenues for predicting the responses of other functional microbial groups to climate change, beneficially or maliciously.

Environmental Sciences & Ecology↗

A Photochemical Phosphorus-Hydrogen-Oxygen Network for Hydrogen-dominated Exoplanet Atmospheres

Due to the detection of phosphine (PH 3 ) in the solar system gas giants Jupiter and Saturn, PH 3 has long been suggested to be detectable in exosolar substellar atmospheres too. However, to date, direct detection of phosphine has proven to be elusive in exoplanet atmosphere surveys. We construct an updated phosphorus-hydrogen-oxygen (PHO) photochemical network suitable for the simulation of gas giant hydrogen-dominated atmospheres. Using this network, we examine PHO photochemistry in hot Jupiter and warm Neptune exoplanet atmospheres at solar and enriched metallicities. Our results show for HD 189733b-like hot Jupiters that HOPO, PO, and P 2 are typically the dominant P carriers at pressures important for transit and emission spectra, rather than PH 3 . For GJ1214b-like warm Neptune atmospheres our results suggest that at solar metallicity PH 3 is dominant in the absence of photochemistry, but is generally not in high abundance for all other chemical environments. At 10 and 100 times solar, small oxygenated phosphorus molecules such as HOPO and PO dominate for both thermochemical and photochemical simulations. The network is able to reproduce well the observed PH 3 abundances on Jupiter and Saturn. Despite progress in improving the accuracy of the PHO network, large portions of the reaction rate data remain with approximate, uncertain, or missing values, which could change the conclusions of the current study significantly. Improving understanding of the kinetics of phosphorus-bearing chemical reactions will be a key undertaking for astronomers aiming to detect phosphine and other phosphorus species in both rocky and gaseous exoplanetary atmospheres in the near future.

atmospheric composition↗

Data and scripts associated with: “Burn severity and vegetation type control phosphorus concentration, molecular composition, and mobilization”

This data package is associated with the publication “Burn severity and vegetation type control phosphorus concentration, molecular composition, and mobilization” published in European Geophysical Union - Biogeosciences (Barnes et al. 2025). This study investigates how phosphorus (P) biogeochemistry is altered by burn severity in contrasting types of vegetation chars. This data package documents the workflow used to process and generate the main figures and statistics in the manuscript. The R scripts reference minimally processed P nuclear magnetic resonance (P-NMR) and X-ray absorption near edge structure (P-XANES) data, as well as fully processed data including total elemental composition of the solid chars, total elemental composition of the char leachates (particulate and aqueous phases), and leachate aqueous phase molybdate reactive P concentration. These source data and associated metadata can be found on ESS-DIVE at https://data.ess-dive.lbl.gov/datasets/doi:10.15485/1894135 (Grieger et al. 2022; v3). Files and scripts included in this data package finish the processing workflow for P-NMR and P-XANES data. These data can be used to gain a better understanding of bulk chemical changes in chars and their leachates, as well as detailed molecular changes to P. This data package is associated with the GitHub repository found at https://github.com/river-corridors-sfa/rcsfa-RC3-BSLE_P. This data package is comprised of a “data” folder and a series of data processing and analysis scripts. Details on how to recreate the workflow can be found in the Critical Details section of the readme and the “workflow_readme.md” file. The file-level metadata file (file ending in “flmd.csv”) lists all files contained in this data package and descriptions for each. The data dictionary (file ending in “dd.csv”) describes all tabular data columns and their respective definitions and units.

54 ENVIRONMENTAL SCIENCES↗

Delayed leaf greening involves a major shift in the expression of cytosolic and mitochondrial ribosomes to plastid ribosomes in the highly phosphorus-use-efficient Hakea prostrata (Proteaceae)

Abstract Background and aims Hakea prostrata (Proteaceae) is a highly phosphorus-use-efficient plant native to southwest Australia. It maintains a high photosynthetic rate at low leaf phosphorus (P) and exhibits delayed leaf greening, a convergent adaptation that increases nutrient-use efficiency. This study aimed to provide broad physiological and gene expression profiles across leaf development, uncovering pathways leading from young leaves as nutrient sinks to mature leaves as low-nutrient, energy-transducing sources. Methods To explore gene expression underlying delayed greening, we analysed a de novo transcriptome for H. prostrata across five stages of leaf development. Photosynthesis and respiration rates, and foliar pigment, P and nitrogen (N) concentrations were determined, including the division of P into five biochemical fractions. Key results Transcripts encoding functions associated with leaf structure generally decreased in abundance across leaf development, concomitant with decreases in foliar concentrations of 85% for anthocyanins, 90% for P and 70% for N. The expression of genes associated with photosynthetic function increased during or after leaf expansion, in parallel with increases in photosynthetic pigments and activity, much later in leaf development than in species that do not have delayed greening. As leaves developed, transcript abundance for cytosolic and mitochondrial ribosomal proteins generally declined, whilst transcripts for chloroplast ribosomal proteins increased. Conclusions There was a much longer temporal separation of leaf cell growth from chloroplast development in H. prostrata than is found in species that lack delayed greening. Transcriptome-guided analysis of leaf development in H. prostrata provided insight into delayed greening as a nutrient-saving strategy in severely phosphorus-impoverished landscapes.

59 BASIC BIOLOGICAL SCIENCES↗

Predicting lake surface water phosphorus dynamics using process-guided machine learning

Phosphorus (P) loading to lakes is degrading the quality and usability of water globally. Accurate predictions of lake P dynamics are needed to understand whole-ecosystem P budgets, as well as the consequences of changing lake P concentrations for water quality. However, complex biophysical processes within lakes, along with limited observational data, challenge our capacity to reproduce short-term lake dynamics needed for water quality predictions, as well as long-term dynamics needed to understand broad scale controls over lake P. Here we use an emerging paradigm in modeling, process-guided machine learning (PGML), to produce a phosphorus budget for Lake Mendota (Wisconsin, USA) and to accurately predict epilimnetic phosphorus over a time range of days to decades. In our implementation of PGML, which we term a Process-Guided Recurrent Neural Network (PGRNN), we combine a process-based model for lake P with a recurrent neural network, and then constrain the predictions with ecological principles. We test independently the process-based model, the recurrent neural network, and the PGRNN to evaluate the overall approach. The process-based model accounted for most of the observed pattern in lake P; however it missed the long-term trend in lake P and had the worst performance in predicting winter and summer P in surface waters. The root mean square error (RMSE) for the process-based model, the recurrent neural network, and the PGRNN was 33.0 μg P L -1 , 22.7 μg P L -1 , and 20.7 μg P L -1 , respectively. All models performed better during summer, with RMSE values for the three models (same order) equal to 14.3 μg P L -1 , 10.9 μg P L -1 , and 10.7 μg P L -1 . Although the PGRNN had only marginally better RMSE during summer, it had lower bias and reproduced long-term decreases in lake P missed by the other two models. For all seasons and all years, the recurrent neural network had better predictions than process alone, with root mean square error (RMSE) of 23.8 μg P L -1 and 28.0 μg P L -1 , respectively. The output of PGRNN indicated that new processes related to water temperature, thermal stratification, and long term changes in external loads are needed to improve the process model. By using ecological knowledge, as well as the information content of complex data, PGML shows promise as a technique for accurate prediction in messy, real-world ecological dynamics, while providing valuable information that can improve our understanding of process.

54 ENVIRONMENTAL SCIENCES↗

Phosphorus replenishment to improve the contact resistivity of light-induced Al contacts on Si solar cells

A method to repair laser-induced phosphorus loss from the n-type emitter of Si solar cells during light-induced Al plating is demonstrated. The ability to add a water-reactive phosphorus compound, PCl 5 , into the Al plating bath gives a unique advantage to Al over Cu for front contacts on Si solar cells. The contact resistivity between light-induced Al and Si emitter is reduced to as low as 0.1 mΩ-cm 2 . Cyclic voltammetry performed on a plating bath composed of 81 wt% 1-ethyl-3-methylimidazolium tetrachloroaluminate, 19 wt% AlCl 3 , and 0.2 wt% PCl 5 reveals multiple reduction reactions of PCl 5 , although incomplete decomposition of PCl 5 is possible. A decrease in nucleation loop size during cyclic voltammetry is also observed suggesting that PCl 5 , while being consumed, modifies the growth mechanism during Al plating. Structural analysis confirms that the addition of PCl 5 produces an Al film which is levelized and compact. Here, a pulsed voltage profile coupled with chemical analysis verifies that phosphorus incorporation is electrolytically activated and is likely the cause for the low contact resistivity.

14 SOLAR ENERGY↗

Nutrient limitation shapes functional traits of mycorrhizal fungi and phosphorus-cycling bacteria across an elevation gradient

In nutrient-limited high-elevation ecosystems, plants rely on arbuscular mycorrhizal (AM) fungi to provide mineral phosphorus (P) in the form of phosphate (PO43-). AM fungi gather these nutrients from phosphorus-cycling bacteria (PCBs) that can mineralize PO43- from organic matter and solubilize mineral-bound P. How climate, soil factors, and nutrient limitation influence AM fungi and PCB assembly remains unclear. We collected soil from montane meadows across a 1,000-m elevation gradient on three replicate mountainsides and analyzed AM fungal marker genes, P-cycling genes from shotgun metagenomes, and edaphic measurements. High-elevation soils had nearly 50-fold less soil PO₄³⁻ and 60% more AM fungal hyphae than low-elevation soils. AM fungal turnover was linked to changes in pH, organic carbon, and PO₄³-. The composition of 198 P-cycling genes was influenced by the AM fungal community structure. Drivers of individual PCB functional genes, including pH and organic carbon, varied with gene phylogeny. We found a trade-off in P-cycling strategies across elevation: P-rich, low-elevation soils supported root-colonizing AM fungi and organic P-mineralizing bacteria. P-poor, high-elevation soils were dominated by stress-tolerant AM fungi and mineral P-solubilizing bacteria. Our results suggest that AM fungi and PCB community turnover across elevation are both shaped by pH, organic carbon, and P availability. With continued climate warming, the structure and function of mountaintop ecosystems might shift to resemble lower elevations, disrupting long-established and specialized microbial assemblages, with consequences for P-cycling dynamics and the total P available to plant communities.IMPORTANCEPhosphorus (P) limits plant productivity in high-elevation ecosystems, yet the microbial networks that mobilize P, including arbuscular mycorrhizal (AM) fungi and phosphorus-cycling bacteria (PCBs), remain under-characterized in these nutrient-poor soils. We show that across a 10,00-m elevation gradient, AM fungi and P-cycling gene assemblages shift predictably with pH, organic carbon, and phosphate availability. Higher elevations, with less available P, select for stress-tolerant AM fungal taxa and PCB strategies geared toward mineral solubilization, while low-elevation sites favor root colonization by AM fungi and organic P mineralization. These results suggest that nutrient limitation can constrain microbial community assembly in consistent ways across landscapes. High mountain soils are low in P and rely on a network of underground AM fungi and PCB to deliver nutrients to plants. This study shows how those underground relationships reorganize with elevation and how climate change could collapse long-standing microbial strategies by pushing high-elevation ecosystems toward lowland conditions. As soils warm and dry, the microbial scaffolding that supports alpine plant life may become increasingly unstable.

arbuscular mycorrhizal fungi↗

Phosphorus sorption and its environmental predictors across pantropical forest soils sampled over the past decade

Tropical forest productivity is frequently constrained by soil phosphorus (P) availability, yet global Land Surface Model (LSM), which are used to simulate ecosystem processes, still represent P cycling in tropical regions only in a limited way, largely because of scarce observational data. Phosphorus adsorption and desorption of dissolved inorganic P to and from soil minerals (hereafter termed sorption), is an important process for predicting how much P is available to plants. This dataset was created to improve predictions of soil P sorption in tropical soils by identifying the isotherm equation that best describes pantropical soils. It includes raw measurements of environmental variables, such as soil properties and climate, together with P sorption data collected from 40 forest soil pits from 9 Forest Global Earth Observatory (ForestGEO) sites across 7 tropical countries during 2018-2022. The data are organized by site, country, and continent. Each site may include several soil pits. For each pit, P sorption was measured across a range of soil P concentrations to build sorption isotherm curves, typically with about 6 to 8 measurements per curve. While sorbed P varies across these concentration levels, the other environmental variables remain constant at the plot level.

Aluminum oxide↗

Mechanochemistry of Phosphorus and Arsenic Alloys for Visible and Infrared Photonics

Incorporating few‐layer 2D phosphorus–arsenic alloys (PAs) into optoelectronic devices requires a synthesis technique that allows control of the alloy composition while producing volumes of material suitable for application development such as photodetectors, solar cells, and lasers. With that goal in mind, high‐energy ball milling allows production of both orthorhombic (o‐PAs) and trigonal (t‐PAs) alloys by reacting red phosphorus and metallic arsenic powders. The synthesis follows a two‐step process in which arsenic rapidly reacts with red phosphorus to first produce t‐PAs followed by a slower phase transformation into o‐PAs; synthesis time and overall conversion rate are slightly enhanced by the presence of arsenic. Optical measurements on exfoliated alloys at the few‐layer atomic limit of the 2D PAs reveal emission spanning from the visible (≈1.9 eV) into the near‐infrared region, covering a broad application space. Rapid powder synthesis within a closed system for stochiometric control of the solid‐solution PAs alloys combined with solution‐based exfoliation opens up opportunities for a whole new class of optoelectronic devices based on PA nanomaterials.

Pedersen, Samuel V.↗

The P( 4 S) + NH( 3 Σ – ) and N( 4 S) + PH( 3 Σ – )reactions as sources of interstellar phosphorus nitride

Phosphorus nitride (PN) is believed to be one of the major reservoirs of phosphorus in the interstellar medium (ISM). For this reason, understanding which reactions produce PN in space and predicting their rate coefficients is important for modelling the relative abundances of P-bearing species and clarifying the role of phosphorus in astrochemistry. Here, in this work, we explore the potential energy surfaces of the $\textrm{P}(^4\textrm{S}) + \textrm{NH}(^3\Sigma^-)$ and $\textrm{N}(^4\textrm{S}) + \textrm{PH}(^3\Sigma^-)$ reactions and the formation of $\textrm{H}(^2\textrm{S}) + \textrm{PN}(^1\Sigma^+)$ through high accuracy ab initio calculations and the variable reaction coordinate transition state theory (VRC-TST). We found that both reactions proceed without an activation barrier and with similar rate coefficients that can be described by a modified Arrhenius equation ( $k(T)=\alpha\!\left( T/300 \right)^{\beta} \exp\!{(\!-\!\gamma/T)})$ with $\alpha=0.93\times 10^{-10}\rm cm^3\,s^{-1}$ , $\beta=-0.18$ and $\gamma=0.24\, \rm K$ for the $\textrm{P} + \textrm{NH} \longrightarrow \textrm{H} + \textrm{PN}$ reaction and $\alpha=0.88\times 10^{-10}\rm cm^3\,s^{-1}$ , $\beta=-0.18$ and $\gamma=1.01\, \rm K$ for the $\textrm{N} + \textrm{PH} \longrightarrow \textrm{H} + \textrm{PN}$ one. Both reactions are expected to be relevant for modelling PN abundances even in the cold environments of the ISM. Given the abundance of hydrogen in space, we have also predicted rate coefficients for the destruction of PN via H + PN collisions.

79 ASTRONOMY AND ASTROPHYSICS↗

Diel partitioning in microbial phosphorus acquisition in the Sargasso Sea

The daily cycle of photosynthetic primary production at the base of marine food webs is often limited by the availability of scarce nutrients. Microbial competition for these scarce resources can be alleviated insofar as the intensity of nutrient uptake and assimilation activities are distributed heterogeneously across organisms over periodic input cycles. Recent analysis of community transcriptional dynamics in the nitrogen-limited subtropical North Pacific gyre revealed evidence of temporal partitioning of nitrogen uptake and assimilation between eukaryotic phytoplankton, cyanobacteria, and heterotrophic bacteria over day-night cycles. Here, we present results from a Lagrangian metatranscriptomic time series survey in the Sargasso Sea and demonstrate temporally partitioned phosphorus uptake in this phosphorus-limited environment. In the Sargasso, heterotrophic bacteria, eukaryotic phytoplankton, and cyanobacteria express genes for phosphorus assimilation during the morning, day, and dusk, respectively. In conclusion, these results support the generality of temporal niche partitioning as an emergent mechanism that can structure uptake of limiting nutrients and facilitate coexistence of diverse microbes in open ocean ecosystems.

biological oceanography↗

Factorial experiment to identify two-way interactions between temperature, harvesting period, hydraulic retention time, and light intensity that influence the biomass productivity and phosphorus removal efficiency of a microalgae–bacteria biofilm

Rotating algae biofilm reactors (RABRs) can reduce energy requirements for wastewater reclamation but require further optimization for implementation at water resource recovery facilities (WRRF). Optimizing RABR operation is challenging because conditions at WRRF change frequently, and disregarding interaction terms related to these changes can produce incorrect conclusions about RABR behavior. This study evaluated the two-way interaction and main effects of four factors on the biomass productivity and phosphorus removal efficiency of a microalgae-bacteria biofilm grown in municipal anaerobic digester centrate, with factor levels and operating conditions selected to mimic a pilot RABR at a WRRF in Utah. Two-way interactions harvesting period*light intensity (LI), harvesting period*temperature, and LI*hydraulic retention time (HRT) had significant effects on biomass productivity: at high temperature and low LI, highest biomass productivity was achieved with a 14-day harvesting period, but at medium temperature and high LI, highest biomass productivity was achieved with a 7-day harvesting period. At high HRT, highest biomass productivity occurred at low LI, but at low HRT, highest biomass productivity occurred at high LI. Phosphorus removal was strongly influenced by LI and occurred most rapidly during the first 2 days HRT, which suggests precipitation contributed significantly to phosphorus removal. These observations provide insight for further RABR optimization.

09 BIOMASS FUELS↗

Development and Validation of a Process Model and Open-Source Process Simulator for Microalgae-Based Tertiary Phosphorus Recovery

Microalgae-based tertiary wastewater treatment has the potential to meet stringent effluent phosphorus limits, with the added benefit of producing a marketable feedstock. However, the lack of validated mechanistic models and their implementation in process simulators have limited the adoption of this technology. In this study, an updated lumped pathway metabolic model (Phototrophic-Mixotrophic Process Model, PM 2 ), including both photoautotrophic and heterotrophic metabolisms of microalgae, was developed to predict effluent phosphorus concentration and biomass yield in response to dynamic influent and varying environmental conditions. The model was implemented in QSDsan – an open-source, Python-based design and simulation platform – for robust simulation under uncertainty. A global sensitivity analysis was performed to prioritize model parameters for calibration. The model was then calibrated and validated using batch experimental data and 45 days of continuous online monitoring data from a full-scale (568 m 3 ·d -1 ) microalgae-based tertiary wastewater treatment plant (EcoRecover process). In particular, along with dynamic influent composition, temperature and light intensity data with diel variation were provided as model inputs to reflect the microalgal behavior under day-night cycling. Overall, the QSDsan-based microalgae process simulator was able to predict effluent phosphorus within 0.02–0.04 mg-P·L -1 , while also capturing the general trends of state variables according to nutrient availability.

Lumped pathway metabolic model↗

Phosphorus-carbon composites as battery anode materials

An electrochemical device includes an anode containing a phosphorus-carbon composite including a conductive carbon matrix and nano-sized phosphorus particles, wherein the nano-sized phosphorus particles are uniformly dispersed on the surface and/or pores of the carbon matrix.

Xu, Guiliang↗

Atomic-Scale Investigation of Oxidation at the Black Phosphorus Surface

Black phosphorus (BP) exhibits extraordinary electronic properties that are desirable for a wide variety of electronic and optoelectronic applications. However, applications of BP are hindered by its rapid degradation in ambient conditions. Despite significant advances that have been made in understanding the degradation mechanism, no consensus has yet been reached on how BP oxidation occurs at the atomic scale as experimental studies have been mostly restricted to averaged effects of degradation over a micron- to millimeter-sized region. Here, BP oxidation is investigated using scanning tunneling microscopy/spectroscopy (STM/S). Introducing O 2 gas to the BP surface in ultrahigh vacuum at a pressure of 10 –5 mbar for 1 min creates two new types of defects on the surface. We identify these defects as dangling atomic oxygen and phosphorus multivacancies using density functional theory simulations. In addition to the structural changes to the surface, the electronic structure is also drastically altered by the introduction of oxygen. The 300 meV band gap of BP is lifted due to dosing. This change in the electronic structure is reversible through STM tip manipulation. As a result, these are the first experimental results showing the atomic-scale oxidation of BP, an important step toward understanding the degradation process

2D materials↗

Zero-Valent Palladium Single-Atoms Catalysts Confined in Black Phosphorus for Efficient Semi-Hydrogenation

Single-atom catalysts (SACs) represent a new frontier in heterogeneous catalysis due to their remarkable catalytic properties and maximized atomic utilization. However, single atoms often bond to the support with polarized electron density and thus exhibit a high valence state, limiting their catalytic scopes in many chemical transformations. In this study, it is demonstrated that 2D black phosphorus (BP) acts as giant phosphorus (P) ligand to confine a high density of single atoms (e.g., Pd 1 , Pt 1 ) via atomic layer deposition. Unlike other 2D materials, BP with relatively low electronegativity and buckled structure favors the strong confinement of robust zero-valent palladium SACs in the vacancy site. Metallic Pd 1 /BP SAC shows a highly selective semi-hydrogenation of phenylacetylene toward styrene, distinct from metallic Pd nanoparticles that facilitate the formation of fully hydrogenated products. Density functional theory calculations reveal that Pd atom forms covalent-like bonding with adjacent P atoms, wherein H atoms tend to adsorb, aiding the dissociative adsorption of H 2 . Zero-valent Pd in the confined space favors a larger energy gain for the synthesis of partially hydrogenated product over the fully hydrogenated one. This work provides a new route toward the synthesis of zero-valent SACs on BP for organic transformations.

36 MATERIALS SCIENCE↗